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Journal of Materials Chemistry B · 2019 ·Vol. 7 ·期 38 ·5789-5796 · IF 5.047

Upper critical solution temperature polymer-grafted hollow mesoporous silica nanoparticles for near-infrared-irradiated drug release

Wei Hu,Xiaowen Bai,Yaping Wang,Zhentao Lei,Haipeng Luo,Zaizai Tong

Near-infrared (NIR) irradiation responsive drug delivery systems have many advantages, which have attracted extensive interest from researchers. In this study, a NIR-triggered drug release system was established by grafting upper critical solution temperature (UCST) polymers on the surface of hollow mesoporous silica nanoparticles (HMSNs) followed by treatment with the photothermal conversion agent indocyanine green (ICG). The as-prepared UCST polymers showed the clearing temperature of 45 °C, which were advantageous to serve as gatekeepers in the physiological environment (37 °C). Under NIR irradiation, the temperature of the solution was elevated above the clearing point due to the presence of ICG; consequently, the collapsed UCST polymer chains became more hydrophilic; this resulted in the exposure of the mesoporous channels of the HMSNs and achievement of a burst drug release. Moreover, this NIR-responsive delivery system showed good biocompatibility and high anticancer efficiency towards the MCF-7 cancer cells upon exposure to NIR irradiation. In addition, a synergistic effect of thermal and chemo treatment has been achieved by the application of NIR irradiation since cancer cells are more vulnerable to high temperatures than normal cells.

研究领域: 材料科学 · 生物医学工程 · 药学
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POLYMER · 2018 · IF 3.483

Poly(imidazoled glycidyl methacrylate-co-diethyleneglycol methyl ether methacrylate) – A new copolymer with tunable LCST and UCST behavior in water

Ganwei Zhang,Jianbin Lei,Longbo Wu,Chenchen Guo,Jialong Fang,Renbi Bai,Ian Wyman

A series of poly (imidazoled glycidyl methacrylate- co -diethylene glycol methyl ether methacrylate) copolymers (denoted as P (iGMA- co -MEO 2 MA)) with different monomer compositions were synthesized and characterized. These copolymers exhibit lower critical solution temperature (LCST) behaviors as the mole ratio of iGMA to MEO 2 MA in the copolymers range from 0/100 to 1/1, and upper critical solution temperature (UCST) behaviors when this mole ratio ranges from 4/1 to 10/1. The thermoresponsive behaviors of these copolymers were also investigated in water at different pH values. The LCST of the copolymer increased with the iGMA content in the copolymer at pH 6.5, and changed little at pH 7.0, while it decreased with the iGMA content in the copolymer at pH 7.5. Meanwhile, the UCST of the copolymer increased with the iGMA content in the copolymer at pH 6.5 and 7.0. In addition, the thermoresponsive properties of P (iGMA- co -MEO 2 MA) were influenced by the presence of salt and by the copolymer concentration. This paper offers a facile approach toward thermoresponsive materials with tunable LCST and UCST behaviors.

研究领域: 高分子化学 · 材料科学
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Advanced Healthcare Materials · 2022 ·Vol. 12 ·期 3 ·2201925 · IF 11.092

Swelling-Mediated Mechanical Stimulation Regulates Differentiation of Adipose-Derived Mesenchymal Stem Cells for Intervertebral Disc Repair Using Injectable UCST Microgels

Xianpeng Huang,Di Chen,Chengzhen Liang,Kesi Shi,Xiaopeng Zhou,Yuang Zhang,Yi Li,Jiangjie Chen,Kaishun Xia,Jiawei Shu,Biao Yang,Jingkai Wang,Haibin Xu,Chao Yu,Feng Cheng,Shaoke Wang,Yongxiang Zhang,Chenggui Wang,Liwei Ying,Hao Li,Meiling Han,Fangcai Li,Yiqing Tao,Qian Zhao,Qixin Chen

Mechanical stimulation is an effective approach for controlling stem cell differentiation in tissue engineering. However, its realization in in vivo tissue repair remains challenging since this type of stimulation can hardly be applied to injectable seeding systems. Here, it is presented that swelling of injectable microgels can be transformed to in situ mechanical stimulation via stretching the cells adhered on their surface. Poly(acrylamide- co -acrylic acid) microgels with the upper critical solution temperature property are fabricated using inverse emulsion polymerization and further coated with polydopamine to increase cell adhesion. Adipose-derived mesenchymal stem cells (ADSCs) adhered on the microgels can be omnidirectionally stretched along with the responsive swelling of the microgels, which upregulate TRPV4 and Piezo1 channel proteins and enhance nucleus pulposus (NP)-like differentiation of ADSCs. In vivo experiments reveal that the disc height and extracellular matrix content of NP are promoted after the implantation with the microgels. The findings indicate that swelling-induced mechanical stimulation has great potential for regulating stem cell differentiation during intervertebral disc repair.

研究领域: 组织工程 · 干细胞生物学 · 生物医学工程 · 骨科
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Science Advances · 2019 ·Vol. 5 ·期 8 · IF 12.804

Off-on switching of enzyme activity by near-infrared light-induced photothermal phase transition of nanohybrids

Song Zhang,Changping Wang,Hong Chang,Qiang Zhang,Yiyun Cheng

The off-on manipulation of enzyme activity is a challenging task. We report a new strategy for reversible off-on control of enzyme activity by near-infrared light. Enzymes acting on macromolecular substrates are embedded with an ultrasmall platinum nanoparticle and decorated with thermoresponsive copolymers, which exhibit upper critical solution temperature (UCST) behavior. The polymer-enzyme nanohybrids form microscale aggregates in solution below the UCST to prevent macromolecular substrates from approaching the enzymes and thus inhibit the enzyme activity, and they disassemble above the UCST to reactivate the enzyme. Upon near-infrared irradiation, platinum nanoparticles inside the enzymes generate heat through a photothermal effect to cause phase transition of the copolymers. Therefore, we can reversibly switch off and on the activities of three enzymes acting on polysaccharide, protein, and plasmid. The enzyme activities are increased by up to 61-fold after laser irradiation. This study provides a facile and efficient method for off-on control of enzyme activity.

研究领域: 生物技术 · 纳米技术 · 酶学 · 材料科学
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JOURNAL OF MOLECULAR LIQUIDS · 2023 · IF 6

Temperature response behavior of poly(1-vinyl-3-methylimidazole dimethyl phosphate-co-N-isopropylacrylamide) in aqueous and ester solutions driven by hydrogen bonding

Zihao Dong,Yajuan Qu,Yuyang Jiao,Ke Xue,Wenguang Zhu,Hai Liu,Jianguang Qi,Yinglong Wang

A series of poly(1-vinyl-3-methylimidazole dimethyl phosphate- co -N-isopropylacrylamide) oligomers was synthesized by reversible addition-fragmentation chain transfer polymerization. The co-oligomers exhibited a pH-tunable lower critical solution temperature (LCST) phase transition in aqueous solutions. By changing the pH of the aqueous solution (HCI), the hydrogen bonding between the internal molecules of the co-oligomers and water molecules was weakened, which effectively reduced the cloud-point temperature. Poly(1-vinyl-3-methylimidazole dimethyl phosphate- co - N -isopropylacrylamide) oligomers exhibit an upper critical solution temperature (UCST) type of phase transition in an ester solution, which is associated with the formation and breaking of hydrogen bonds within the co-oligomers molecules. FT-IR analysis revealed the effect of temperature on hydrogen bonding between the functional groups. Energy decomposition, Electrostatic Potential (ESP), Atoms-in-Molecules (AIM), and Interaction region indicator (IRI) analyses demonstrated the presence of hydrogen bond donors N–H and imidazole ring C–H, and hydrogen bond acceptors C = O and P = O in the co-oligomers. The sites of hydrogen bonding between the co-oligomers and the solvent molecules as well as intermolecular forces were found to be the main factors contributing to the LCST/UCST-type phase transition.

研究领域: 高分子化学 · 物理化学
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POLYMER · 2020 · IF 4.231

Novel thermoresponsive homopolymers of poly[oligo(ethylene glycol) (acyloxy) methacrylate]s: LCST-type transition in water and UCST-type transition in alcohols

Ke Wang,Qi Liu,Guiyan Liu,Yongfei Zeng

The study of thermoresponsive homopolymers has attracted great attention due to their broad application value. Herein, a series of novel thermoresponsive homopolymers of poly[oligo(ethylene glycol) (acyloxy) methacrylate]s containing oligo(ethylene glycol) (OEG) units and substituent groups of ester have been designed and prepared by RAFT polymerization . The solution properties of these polymers have been investigated in detail, which indicate that most of them exhibit lower critical solution temperature (LCST) in water and upper critical solution temperature (UCST) in alcohols, and their LCST-type or UCST-type cloud point temperature ( T CP L TCPL or T CP U TCPU ) is closely related to the OEG units and ester groups. Furthermore, the parameters affecting the thermoresponse of these polymers including polymerization degree (DP) and concentration have also been investigated. The present work not only discovers a series of novel thermoresponsive polymers, but also has certain guiding significance on the understanding of molecular structure and thermoresponsive property relationships, which is useful for the design of new thermosensitive polymers.

CAS / MDL: 920-46-7
研究领域: 高分子化学 · 材料科学
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MACROMOLECULES · 2023 · IF 5.5

Color-Shifting Fluorescent System Based on an AIE Polymer with an Upper Critical Solution Temperature

Shunfeng Yu,Kang Liu,Yueyi Tian,Xiaoxiao Chen,Jie Zhang,Mei Gao,Jinhui Wang,Mingming Zhang,Chuanzhuang Zhao

The design of thermoresponsive luminescent polymers with both a tunable upper critical solution temperature (UCST) and a tunable color is of great challenge. Herein, a series of thermoresponsive copolymers with UCST and aggregation-induced emission (AIE) behaviors are prepared, and a color-shifting fluorescent system based on the energy conversion between the AIE polymers and fluorescent dyes is constructed. The copolymers are prepared from acrylamide and 6-(4-vinylphenyl)-2,4-diamino-1,3,5-triazine (VPhDT). Benefitting from VPhDT, an AIE-active monomer that can provide multiple hydrogen bonds and enhance association of the polymer chains, the obtained copolymers exhibit both UCST and AIE behaviors in aqueous solutions. Utilizing the AIE copolymers as the donor and fluorescent dyes as the acceptors, color-shifting fluorescent systems that can emit blue, green, and red lights are established. The color-shifting fluorescent systems also exhibit tunable luminescent intensities and colors with the stimuli of temperature and pH. Such a color-shifting fluorescent system may have promising applications in the fields of temperature sensors and information displays.

CAS / MDL: 79-06-1 64-17-5
研究领域: 聚合物化学 · 材料科学 · 光学材料 · 纳米技术
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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 34 ·14551-14559 · IF 3.288

A pH and UCST thermo-responsive tri-block copolymer (PAA-b-PDMA-b-P(AM-co-AN)) with micellization and gelatinization in aqueous media for drug release

Cheng Zhou,Yan Chen,Mingjun Huang,Yi Ling,Liming Yang,Guochen Zhao,Jie Chen

A brand new pH and thermo-responsive amphiphilic ABC triblock copolymer of poly(acrylic acid)-block-poly(N,N-dimethyl acrylamide)-block-poly(acrylamide-co-acrylonitrile) (PAA-b-PDMA-b-P(AM-co-AN)) was synthesized via sequential reversible addition–fragmentation chain transfer (RAFT) polymerization. Due to the pH-responsive blocks of PAA and thermo-responsive blocks of P(AM-co-AN), the properties of the copolymer solution were controlled by varying parameters such as temperature and pH. Specifically, it formed different nanostructures and showed gel behavior under different conditions. In detail, under high temperature alkaline conditions, ADAA was dissolved in an aqueous solution in the form of a molecular chain. Thereafter, when the temperature became lower or pH became acidic, the triblock copolymer self-assembled into different micelle structures, including shell–core, core–shell–core and tighter core–linking–core nanoparticles. In addition, the phase transition temperature of the copolymer was adjusted by pH and concentration. When the copolymer hydrogel was injected into a simulated human body device, it showed sustained drug release behavior and low transient drug concentrations. MTT experiments demonstrated the good biocompatibility of the ADAA hydrogels. This research provides inspiration to develop new polymers which are expected to be promising candidates as part of drug delivery platforms. Compared with traditional responsive hydrogels, its UCST can be easily controlled and is more stable through the feeding ratio, making it more advantageous in human drug delivery applications. In summary, we believe that this UCST and pH-responsive injectable ADAA hydrogel is researchable and applicable in the biomedical field.

研究领域: 材料科学 · 生物医学工程 · 药学
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JOURNAL OF CONTROLLED RELEASE · 2024 · IF 10.5

NIR-triggered and Thermoresponsive Core-shell nanoparticles for synergistic anticancer therapy

Hong Zhang,Xiao Wang,Xiaorong Yang,Zehua Wu,Qin Chen,Qiaolin Wei,Yong Guo,Quan Hu,Jia-Wei Shen

Recent advancements in cancer treatment have underscored the inadequacy of conventional monotherapies in addressing complex malignant tumors. Consequently, there is a growing interest in synergistic therapies capable of overcoming the limitations of monotherapies, leading to more personalized and effective approaches. Among these, the combination of photothermal therapy (PTT) and chemotherapy has emerged as a promising avenue for tumor management. In this study, we present a novel approach utilizing thermoresponsive mesoporous silica nanoparticles (MSN) as a delivery system for the chemotherapeutic drug doxorubicin. By incorporating photothermal agent copper sulfide (CuS) nanoparticles into the MSN, the resulting composite material exhibits potent photothermal properties. Furthermore, the integration of an upper critical solution temperature (UCST) polymer within the silica outer layer serves as a “gatekeeper”, enabling precise control over drug release kinetics. This innovative nanomaterial effectively merges thermoresponsive behavior with PTT, thereby minimizing the collateral damage associated with traditional chemotherapy on healthy tissues. Moreover, in both in vitro studies using mouse breast carcinoma cells (4 T1) and in vivo experiments utilizing a 4 T1 tumor-bearing mouse model, our nanomaterials demonstrated synergistic effects, enhancing the anti-tumor efficacy of combined PTT and chemotherapy. With its remarkable photothermal conversion efficiency, robust stability, and biocompatibility, the UCST-responsive nanoplatform holds immense potential for clinical applications.

CAS / MDL: 298-93-1
研究领域: 纳米技术 · 癌症治疗 · 材料科学 · 生物医学工程
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CHEMISTRY OF MATERIALS · 2020 · IF 9.567

Dual Cross-Linked Ion-Based Temperature-Responsive Conductive Hydrogels with Multiple Sensors and Steady Electrocardiogram Monitoring

Yun Tan,Yuyuan Zhang,Yanjing Zhang,Jun Zheng,Huiqiong Wu,Yang Chen,Shimei Xu,Junliang Yang,Chuntai Liu,Yi Zhang

To balance the requirements of transparency, mechanical strength, stable conductivity, and biocompatibility of traditional electronic conductive hydrogels in intelligent devices is still a formidable challenge. The increase of ionic conductive gels has provided decent transparency, stretchability, and wearability in artificial skins but the dilemma still exists between stability and functionality. This article reports a facile strategy to develop a visual thermosensitive physically and chemically dual cross-linked ion-based conductive hydrogel through in situ free-radical copolymerization, achieving robust mechanical properties, an obvious response, and a multiple sensing process. As an archetypical template, the ion-based conductive hydrogel offers an evaluation and monitoring of electrocardiogram (ECG), which is comparable to commercial electrodes. Intriguingly, such kinds of conductive gels exhibit tunable upper critical solution temperature (UCST) behaviors. Taking advantage of their high temperature responsive accuracy, the visualized qualitative observation for smart response and digitized measurement and calibration for thermal stimulus can be simultaneously achieved. We therefore believe that this work will inspire the design of skinlike sensing materials, promote the preparation of biocompatible and multiple sensing abilities and the synthesis of intelligent hydrogels, and realize their applications in biosensors, wearable devices, and biomedicine.

研究领域: 材料科学 · 生物医学工程 · 纳米技术 · 传感器 · 可穿戴技术
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